6-Methyl-4-oxo-4H-chromene-3-carbaldehyde

Yousuf, S.; Mukhtar, A.; Ambreen, N.; Saad, S.M.; Khan, K.M.

doi:10.1107/S1600536812037555

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2920

https://doi.org/10.1107/S1600536812037555

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6-Methyl-4-oxo-4H-chromene-3-carbaldehyde

Sammer Yousuf,^a ^* Asma Mukhtar,^a Nida Ambreen,^a Syed Muhammad Saad ^a and Khalid M. Khan ^a

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 28 August 2012; accepted 31 August 2012; online 12 September 2012)

In the title compound, C₁₁H₈O₃, the benzopyran-4-one or chromone ring system is almost planar, with a maximum deviation of 0.045 (2) Å. The crystal structure is stablized by π–π interactions between the benzene and pyran rings of inversion-related molecules stacked along the b axis, with a centroid–centroid distance of 3.5463 (12) Å

Related literature

For the biological activity of chromone, see: Patel et al. (2011 ); Khan et al. (2009 , 2010 ); Gautam et al. (2010 ); Ishar et al. (2006 ); Hassan (1992 ); Nohara et al. (1974 ). For a related structure, see: Wang & Kong (2007 ).

Experimental

Crystal data

C₁₁H₈O₃
M_r = 188.17
Triclinic, $[P \overline 1]$
a = 6.6945 (7) Å
b = 7.1079 (7) Å
c = 10.3032 (11) Å
α = 71.593 (2)°
β = 84.962 (2)°
γ = 69.843 (2)°
V = 436.57 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 273 K
0.26 × 0.23 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.973, T_max = 0.989
4974 measured reflections
1629 independent reflections
1300 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.152
S = 1.07
1629 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812037555/rz2798sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037555/rz2798Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037555/rz2798Isup3.cml

checkCIF report

Comment top

Chromone is a heterocyclic compound containing a benzene ring fused with a pyran ring, so it is also called as benzopyran-4-one. Chromone moieties are associated with various physiological and biological properties such as antibacterial (Patel et al., 2011), antioxidant (Gautam et al., 2010; Hassan et al., 1992), antianaphylactic (Nohara et al., 1974), antiinflammatory (Khan et al., 2010), anticancer (Ishar et al., 2006), and thymidine phosphorylase inhibitor (Khan et al., 2009) activities. The title compound is a chromone derivative synthesized as a part of our ongoing research to study different biological activities of this medicinally important class of organic compounds and establish their structure–activity relationship.

The structure of title compound (Fig. 1) is composed of a planar chromone moiety (O1/C1–C9) with maximum deviation of 0.045 (2) Å for atom C8. Bond lengths and angles are similar to those observed in a structurally related compound (Wang & Kong, 2007). In the crystal (Fig. 2), inversion-related molecules are linked along the b axis by significant π–π stacking interactions occurring between benzene and pyran rings of chromone moeities, with centroid-centroid distances of 3.5463 (12) Å.

Related literature top

For the biological activity of chromone, see: Patel et al. (2011); Khan et al. (2010); (2009); Gautam et al. (2010); Ishar et al. (2006); Hassan (1992); Nohara et al. (1974). For a related structure, see: Wang & Kong (2007).

Experimental top

The title compound was synthesized by taking dry dimethylformamide (12.32 ml) into a three necked flask followed by slow addition of POCl₃ (49 mmol) with intensive stirring at 50°C. Heating and stirring was continued for 2 h at 45–55°C. A solution of 5-methyl-2-hydroxyacetophenone (10 mmol) in DMF was then slowly added under stirring at 50°C. The stirring was continued for additional 2 h at 55–60°C. After cooling, the mixture was kept over night at room temperature and diluted slowly by adding crushed ice (300 g) and stirred again for 6 h to obtain the crude product. Recrystallization from ethanol afforded crystals in 78.7% yield (1.48 g) which were found suitable for single-crystal X-ray diffraction studies. All chemicals were purchased by sigma Aldrich Germany.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the a axis.

6-Methyl-4-oxo-4H-chromene-3-carbaldehyde top

Crystal data top

C₁₁H₈O₃	Z = 2
M_r = 188.17	F(000) = 196
Triclinic, P1	D_x = 1.431 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6945 (7) Å	Cell parameters from 1636 reflections
b = 7.1079 (7) Å	θ = 3.2–28.1°
c = 10.3032 (11) Å	µ = 0.11 mm⁻¹
α = 71.593 (2)°	T = 273 K
β = 84.962 (2)°	Block, colorles
γ = 69.843 (2)°	0.26 × 0.23 × 0.11 mm
V = 436.57 (8) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1629 independent reflections
Radiation source: fine-focus sealed tube	1300 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scan	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.973, T_max = 0.989	k = −8→8
4974 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.0852P)² + 0.0886P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1629 reflections	Δρ_max = 0.26 e Å⁻³
128 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (9)

Crystal data top

C₁₁H₈O₃	γ = 69.843 (2)°
M_r = 188.17	V = 436.57 (8) Å³
Triclinic, P1	Z = 2
a = 6.6945 (7) Å	Mo Kα radiation
b = 7.1079 (7) Å	µ = 0.11 mm⁻¹
c = 10.3032 (11) Å	T = 273 K
α = 71.593 (2)°	0.26 × 0.23 × 0.11 mm
β = 84.962 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1629 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1300 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.989	R_int = 0.019
4974 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.07	Δρ_max = 0.26 e Å⁻³
1629 reflections	Δρ_min = −0.19 e Å⁻³
128 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.2834 (2)	0.1857 (2)	0.62203 (13)	0.0573 (4)
O2	−0.30931 (18)	0.3149 (2)	0.47149 (12)	0.0476 (4)
O3	−0.2182 (3)	0.2434 (3)	0.87960 (15)	0.0749 (5)
C1	0.2333 (3)	0.2150 (3)	0.34035 (18)	0.0415 (4)
H1A	0.3724	0.1795	0.3703	0.050*
C2	0.1952 (3)	0.2394 (3)	0.20506 (19)	0.0455 (5)
C3	−0.0162 (3)	0.2971 (3)	0.16259 (19)	0.0497 (5)
H3A	−0.0452	0.3169	0.0717	0.060*
C4	−0.1816 (3)	0.3252 (3)	0.25048 (19)	0.0494 (5)
H4A	−0.3210	0.3642	0.2199	0.059*
C5	−0.1371 (3)	0.2942 (3)	0.38609 (18)	0.0397 (4)
C6	−0.2734 (3)	0.2855 (3)	0.60304 (19)	0.0443 (5)
H6A	−0.3894	0.2953	0.6604	0.053*
C7	−0.0835 (3)	0.2431 (3)	0.65872 (18)	0.0396 (4)
C8	0.1067 (3)	0.2197 (3)	0.57661 (18)	0.0386 (4)
C9	0.0686 (3)	0.2422 (2)	0.43295 (17)	0.0360 (4)
C10	0.3734 (4)	0.2037 (4)	0.1063 (2)	0.0654 (6)
H10A	0.5069	0.1645	0.1524	0.098*
H10B	0.3537	0.3308	0.0316	0.098*
H10C	0.3733	0.0931	0.0717	0.098*
C11	−0.0697 (3)	0.2176 (3)	0.8057 (2)	0.0548 (5)
H11A	0.0649	0.1784	0.8440	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0400 (8)	0.0876 (10)	0.0504 (8)	−0.0238 (7)	−0.0042 (6)	−0.0252 (7)
O2	0.0330 (7)	0.0611 (8)	0.0441 (7)	−0.0130 (6)	−0.0026 (5)	−0.0121 (6)
O3	0.0733 (11)	0.1117 (13)	0.0537 (9)	−0.0380 (10)	0.0201 (8)	−0.0413 (9)
C1	0.0385 (9)	0.0444 (10)	0.0434 (10)	−0.0157 (8)	0.0003 (7)	−0.0138 (8)
C2	0.0522 (11)	0.0442 (10)	0.0401 (10)	−0.0176 (8)	0.0025 (8)	−0.0117 (8)
C3	0.0609 (12)	0.0530 (11)	0.0348 (9)	−0.0209 (9)	−0.0073 (8)	−0.0087 (8)
C4	0.0436 (10)	0.0553 (11)	0.0459 (11)	−0.0163 (9)	−0.0118 (8)	−0.0077 (8)
C5	0.0373 (9)	0.0369 (9)	0.0423 (10)	−0.0120 (7)	−0.0017 (7)	−0.0085 (7)
C6	0.0389 (10)	0.0465 (10)	0.0440 (10)	−0.0114 (8)	0.0043 (7)	−0.0133 (8)
C7	0.0419 (10)	0.0387 (9)	0.0403 (10)	−0.0145 (7)	0.0017 (8)	−0.0141 (7)
C8	0.0369 (9)	0.0385 (9)	0.0427 (9)	−0.0131 (7)	−0.0033 (7)	−0.0137 (7)
C9	0.0372 (9)	0.0325 (8)	0.0384 (9)	−0.0124 (7)	−0.0024 (7)	−0.0094 (7)
C10	0.0634 (14)	0.0885 (16)	0.0457 (11)	−0.0245 (12)	0.0091 (10)	−0.0256 (11)
C11	0.0550 (12)	0.0696 (13)	0.0482 (11)	−0.0241 (10)	0.0037 (9)	−0.0262 (10)

Geometric parameters (Å, º) top

O1—C8	1.227 (2)	C4—H4A	0.9300
O2—C6	1.335 (2)	C5—C9	1.385 (2)
O2—C5	1.383 (2)	C6—C7	1.339 (3)
O3—C11	1.196 (2)	C6—H6A	0.9300
C1—C2	1.385 (3)	C7—C8	1.455 (2)
C1—C9	1.396 (2)	C7—C11	1.475 (3)
C1—H1A	0.9300	C8—C9	1.473 (2)
C2—C3	1.399 (3)	C10—H10A	0.9600
C2—C10	1.505 (3)	C10—H10B	0.9600
C3—C4	1.368 (3)	C10—H10C	0.9600
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.387 (3)

C6—O2—C5	117.99 (13)	C6—C7—C8	120.85 (16)
C2—C1—C9	121.75 (17)	C6—C7—C11	118.72 (16)
C2—C1—H1A	119.1	C8—C7—C11	120.43 (16)
C9—C1—H1A	119.1	O1—C8—C7	123.32 (16)
C1—C2—C3	117.68 (17)	O1—C8—C9	122.63 (16)
C1—C2—C10	121.76 (18)	C7—C8—C9	114.04 (15)
C3—C2—C10	120.56 (17)	C5—C9—C1	118.08 (16)
C4—C3—C2	122.15 (17)	C5—C9—C8	119.66 (16)
C4—C3—H3A	118.9	C1—C9—C8	122.26 (16)
C2—C3—H3A	118.9	C2—C10—H10A	109.5
C3—C4—C5	118.60 (17)	C2—C10—H10B	109.5
C3—C4—H4A	120.7	H10A—C10—H10B	109.5
C5—C4—H4A	120.7	C2—C10—H10C	109.5
O2—C5—C9	122.29 (16)	H10A—C10—H10C	109.5
O2—C5—C4	116.01 (15)	H10B—C10—H10C	109.5
C9—C5—C4	121.69 (16)	O3—C11—C7	125.06 (19)
O2—C6—C7	125.04 (16)	O3—C11—H11A	117.5
O2—C6—H6A	117.5	C7—C11—H11A	117.5
C7—C6—H6A	117.5

C9—C1—C2—C3	1.3 (3)	C6—C7—C8—C9	−1.3 (2)
C9—C1—C2—C10	−178.14 (16)	C11—C7—C8—C9	177.95 (15)
C1—C2—C3—C4	−1.3 (3)	O2—C5—C9—C1	176.96 (14)
C10—C2—C3—C4	178.17 (18)	C4—C5—C9—C1	−1.9 (3)
C2—C3—C4—C5	−0.3 (3)	O2—C5—C9—C8	−3.7 (3)
C6—O2—C5—C9	0.8 (2)	C4—C5—C9—C8	177.44 (15)
C6—O2—C5—C4	179.73 (15)	C2—C1—C9—C5	0.3 (3)
C3—C4—C5—O2	−176.99 (15)	C2—C1—C9—C8	−179.10 (15)
C3—C4—C5—C9	2.0 (3)	O1—C8—C9—C5	−175.79 (16)
C5—O2—C6—C7	2.0 (3)	C7—C8—C9—C5	3.7 (2)
O2—C6—C7—C8	−1.6 (3)	O1—C8—C9—C1	3.6 (3)
O2—C6—C7—C11	179.14 (16)	C7—C8—C9—C1	−176.89 (14)
C6—C7—C8—O1	178.25 (17)	C6—C7—C11—O3	−4.4 (3)
C11—C7—C8—O1	−2.5 (3)	C8—C7—C11—O3	176.35 (19)

Experimental details

Crystal data
Chemical formula	C₁₁H₈O₃
M_r	188.17
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	6.6945 (7), 7.1079 (7), 10.3032 (11)
α, β, γ (°)	71.593 (2), 84.962 (2), 69.843 (2)
V (Å³)	436.57 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.26 × 0.23 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.973, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	4974, 1629, 1300
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.152, 1.07
No. of reflections	1629
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Acknowledgements

The authors are thankful to OPCW, The Netherlands, and the Higher Education Commission (HEC) Pakistan (project No. 1910) for their financial support.

References

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